Monoazo-dyestuffs of the pyrazolone series



fiatented Aug. 5, 1952 UNITED STATE MoN-o zo-DYEsrUFFs or rail Y PYRAZOLONE seams Willy Widmer, Bottmingen,

Alfred Fasciati, Basel, i

and Ernst Reich, Neuewelt, Munchenstein, Switzerland, assignors to Oiba Limited,Basel,

Switzerland N0 Drawing. Appllcat rial No. 74,234. In

5 Claims. (01. 260163) According to this invention valuable new monoazo-dyestuffs of the pyrazolone series are made by coupling a diazo-compound of an amine of the general formula in which as represents a sulfonamide group in paraposition to one of the groups --COOH and -NH2, with a pyrazolone of the general formula I CH3 in which R represents an aromatic radical of the benzene series, and Z represents a sulfonamide group, and so choosing the starting materials that at least one of the two sulfonamide groups in the dyestuff molecule contains a hydrocarbon radical bound to the nitrogen atom, that the hydrocarbon radical or radicals of the two sulfon amide groups contains or contain together at most 9 carbon atoms, and that the starting materials contain no carboxyl or sulfonic acid groups apart from the single carbowl group present in the diazo-component. r

The 2-aminobenzenel-carboxylic acid sulfonamides of the above formula used as starting materials may contain the sulfonamide group in the 4- or advantageously the 5-position. These compounds can be obtained by methods in themselves known, for example, by reacting a Z-chlorobenzene-l-carboxylic acid-4- or -5-su1fonic acid chloride with ammonia or a primary or secondary amine (appropriately chosen having regard to the foregoing requirements), and exchangingthe chlorine atom in the resulting product for an NH2 group. Z-aminobenzene 1 carboxylic acidl-sulfonamide can also be obtained by heating a l-nitro-Z-methylbenzene-5sulfonamide in a medium containing an alkali hydroxide.

As examples of Z-aminobenzene-l-carboxylic acid-sulfonamidesserving as starting materials and obtainable as described in the preceding paragraph there may be mentioned:

ion February 2,.1949, se- Switzerland February '12,

2 2- aminobenzene -5- sulfonamide acid,

z-aminobenzene -5- sulfonmethylamide -l-: m;

boxylic acid,' r 2- aminobenzene 5 sulfon-isopropylamide'-lcarboxylic acid,

2-aminobenzene-5-sulfon-n-propylamide l care;-

boxylic acid,

Z-aminobenzene -5- sulfon-n-butylamide-l-carboxylic acid,

2-aminobenzene -5- sulfon-di-isopropylamide-lcarboxylic acid,

2- aminobenzene -5- sulfon-di-n-butylamide -1- carboxylic acid,

z-aminobenzene -5- sulfon-n-hexylamide-1-car boxylic acid,

boxylic acid,

Z-aminobenzene -5- sulfon cyclohexylamide-l carboxylic acid,

Z-aminobenzene -5- sulfon-benzylamide -1- carboxylic acid,

2- arrainobenzene-B- sulfon-anilide-l carboxylic 2- aminobenzene -5- sulfon N-methylanilide -1- carboxylic acid, 1

2-aminobenzene -4- sulfon-n-butylamide-l-car;

boxylic acid,

Z-aminobenzene -4- sulfon isopropylamide-l g carboxylic acid. In the pyrazolones of the general formula ilN-'RZ 110 C=NI (3H3 also used as starting materials, the radical R may contain further substituents such, for example, as

alkyl groups, especially methyl groups, or halogen atoms such as chlorine, or nitro groups, alk oxy groups, etc. Such pyrazolones are obtained in known manner, for example,'from ethyl acetovI acetate and an arylhydrazine, which latter may be derived, for example, from one of the following amines: 3-aminobenzene-l-sulfonamide, 3- aminobenzene -1- sulfonmethylamide, 3-aminobenzene -1- sulfon-n-propylamide, B-aminobenzene-1-sulfon-iso-propylamide, 3-aminobenzenel-sulfon-n-butylamide, 3-aminobenzene -lsulfon-diethylamide, 3-aminobenzene-l-sulfon-anilide, 3-aminobenzene -lsulfon-N-ethyl-anilide, 3- amino -4- methylbenzene -1- sulfonamide, 3-

amino-4-chlorobenzene l-sulfonamide, S-aminm -1- carboxylic 2- aminobenzene-5-sulfon-iso-amylamide-1-carr"= 4-methylbenzene -1- sulfon-iso-propylamide, 3- amino-4-chlorobenzene-l-sulfon-ethylamide.

In accordance with this invention both the diazo-component and: the pyrazolone contain a sulfon-amide, group. At least one of these two sulfonamide groups contains a hydrocarbon radical bound to the nitrogen atom. However, more than one of the four substitution positions present in the sulfonamide groups taken together may be occupied by hydrocarbon radicals.

As will be seen from the list of starting materials given above, there come into consideration as hydrocarbon radicals normal or branched alkyl groups, cycloalkyl groups, aromatic radicals of the benzene series and aralkyl groups.

The hydrocarbon radicals present in'the-two sul-.

I OH:

in' which R represents an aromatic radical of the benzene series free from carboxyl, and sulfonic acid. groups, and advantageously represents. the

radical scam,

The use of this'group of pyrazolones necessitates the presence of at least one hydrocarbon radical as a substituent at the nitrogen atom of the sulfonamide group in the diazo component. As diazo components in this connection there come into consideration, for example, amines ofthe-general formula (I) O OH NH2 O=B ll/Yr in which Y1 represents an alkyl, cycloalkyl, aralkyl or aryl group and Y2 represents hydrogen or. analkyl group.

There are advantageously used diazo components, of the general formula coon NET 0 O=i in which Y represents ahydrocarbon radical containing 3-6 carbon atoms, for example, a hexyl, cyclohexyl, amyl, phenyl or advantageously a butyl (for example, n-butyl) or propyl (for example,.isopropyl) group.

The diazotization of the amines used as starting materials in the present invention may be carried out by methods in themselves known, and advantageously by the so-called indirect method, that is to say by uniting a solution which contains analkali salt of the diazo component and also thenecessary quantity of nitrite with a dilute solution of'acid, especially hydrochloric acid, containing a quantity of acid in excess of the theoretical quantity.

In the present process the coupling is advantageously conducted in an alkaline medium. This may be carried out, for example, by dissolving the pyrazolone to be used as coupling component with the quantity of alkali hydroxide required for dissolution, and adding the excess of alkali required for the coupling reaction in the form of an alkali carbonate. If desired, the coupling may also. be carried out with the addition of a neutral or basic solvent, for example, alcohol, pyridine, ethanolamine, etc.

The monoazo dyestufis of the pyrazolone series obtainable by the present process are new. They are free from sulfonic acid groups, contain a single carboXyl group and correspond to the general formula in which one unsubstituted carbon atom is between a: and the nearest of the other substituents.

R represents an aromatic radical of the benzene series and a: and Z each represent a sulfonamide group of which groups at least one con.- tairis a hydrocarbon radical bound to the/nitrogen atom and the hydrocarbon radicals. contain together at most 9 carbon atoms.

The new products canbe used' for dyeing or printing various materials, principally those of animal origin, such as wool, silk and leather, and artificial fibers of superpolyamides or superpol'yurethanes. Especially valuable results are obtained by treating the dyestuffs obtainable. by the present process with agents yielding metal. This treatment may be carried outin known manner in substance or in the dyebath or on the fiber. Thus the metallization may be carried out insubstance, for example, with an agent yielding chromium in a weakly acid, neutral or alkaline medium, if desired in the presence oi suitableadditions,- for example, aromatic ortho-oxy-cav boxylic acids, or bases, organic solvents such as alcohols, or further additions which assist the formation of the complexes, and under atmospheric or superatmospheric pressure. The-metallization in the dyebath or on the fiber may also be carried out in known manner, for example, with the addition of an alkali chromateand anammonium salt.

.By th present process there are-usuallyobtained dyestuffs which are valuable in that they dye wool by the usual chroming processes yellow tints which are very fast, especially to light. The dyestufis are suitable above all for dyeing -by processes in which the dyeing 1S'COIIdUCtvEd 5.. by the single bath process with a solution containing the dyestuff, an alkali chromate and ammonium sulfate. Such processes are known, for example, under the names Synchromate Process and, Metachrome Process. The dyestuffs of the present invention are therefore distinguished from the known products described in U. S. Patent No. 1,821,938 which are of similar constitution, but contain a sulfonic acid group in the radical of the coupling component and are not suitable for dyeing by the single bath chroming process.

The following examples illustrate the invention, the parts being by weight:

Example 1 30.6 parts of 2-aminobenzene-5-sulfon-N- methyl-anilide-l-carboxylic acid are dissolved in 300 parts of water with the addition of 8 parts of anhydrous sodium carbonate. After the introduction of '7 parts of sodium nitrite, the solution is run into a mixture consisting of 40 parts of hydrochloric acid of 30 per cent. strength and sumcient ice to keep the reaction temperature at about 1015 C. during the diazotization, and the whole is stirred until diazotization is complete. The suspension of the diazo-compound is coupled with a solution of 25.3 parts of 1- (3-su1fonamido) -phenyl-3-methyl-5-pyrazclone in 200 parts of Water, 6 parts of sodium hydroxide and 25 parts of anhydrous sodium carbonate at 5-10 C. The whole is stirred until coupling is complete and the dyestuff is separated by filtration. It corresponds to the formula HO COOH I C-N N=N-C ONE g C 2 z OH: O CH:

When dry it is an orange-yellow substance which dissolves in hot water and hot sodium carbonate solution with a yellow coloration, and dyes wool from an acid bath yellow tints which when afterchromed become brownish yellow and very fast to washing, fulling and light. The dyestuflf is excellently suited for dyeing by the single bath chroming process.

. Example 2 27.2 parts of 2-aminobenzene sulfon-nbutylamide-l-carboxylic acid are dissolved in 300 parts of water with the addition of 8 parts of anhydrous sodium carbonate. After introducing 7 parts of sodium nitrite, the solution is run into a mixture consisting of 40 parts of hydrochloric acid of 30 per cent. strength and sufficient ice to keep the reaction temperature at about ill- C. during the diazotization, and the whole is stirred until diazotization is complete, The suspension of the diazo-compound is coupled with a solution of 25.3 parts of 1-(3- sulfonamido) phenyl-B-methyl-5-pyrazolone in 200 parts of water, 6, parts of sodium hydroxide and parts of anhydrous sodium carbonate at 5-10 C. r The whole is'stirred until coupling is complete, and the dyestuif is separated by tration. It corresponds to the formula HO CODE 5 N N=N-C l O S z a ll 0:8 I

I CHs N-CH -CHg-CH -OHs Example 3 29.2 parts of 2-aminobenzene-5-sulfonanilidel-carboxylic acid are dissolved in 300 parts of water with the addition of 8 parts of anhydrous.

sodium carbonate. After the addition of 7 parts of sodium nitrite the solution is run into a mixture consisting of 40 parts of hydrochloric acid of 30 per cent. strength and sufficient ice to keep the reaction temperature at about l0-15 C. during th diazotization, and the whole is stirred until diazotization is complete. The suspension of the diazo-compound is coupled with a solution of 25.3 parts of 1-(3'-sulfonamido)-pheny1- B-methyl-S-pyrazolone in 200 parts of water, 6 parts of sodium hydroxide and 25 parts of anhydrous sodium carbonate at 5-10 C. The whole is stirred until coupling is complete and the dyestuff is separated by filtration. It corresponds to the formula The dyestuff is then stirred in 300 parts of water, and a sufiicient quantity of sodium hydroxide solution of 30 per cent. strength is added to cause complete dissolution. The solution is evaporated to dryness under reduced pressure. There is obtained an orange-yellow substance which dissolves well in cold water and dyes wool from an acid bath yellow tints which when afterchromed become brownish yellow and'very fast to washing, fulling and. light. The dyestuif is excellently suited to dyeing by the single bath chroming process.

By coupling the diam-components given in column 1 of the following table (in the manner described in the foregoing examples) with their respective coupling components given in column 2, there are likewise obtained dyestuffs which yield yellow tints on wool by the after-chroming process or by the single bath chroming process. Among these dyestuifs those which contain in the phenyl radical of the pyrazolone in' addition to the sulfonamide group, a further substitu- O o=li l.

; ent (Cl, CH3) in ortho-position to the linkage to slum bichromate is added, th whole is again brought to the boil, and chroming is carried on at the boil for 40 minutes. The wool is dyed a fast yellow tint.

Example A dyebath is prepared with 1.5 parts of potassium chromate, 1.5 parts of ammonium sulphate, parts of crystalline sodium sulphate and 2 parts of the dyestufi obtained as described in Example 2. 100 parts of well wetted wool are entered into the dyebath at 60 C., the temperature is raised to the boil in the course of 30 minutes, and boiling is continued for 45 minutes. 0.5 part of acetic acid of 40 per cent strength is then added and the whole is boiled for a further 45 minutes. The wool is dyed a very fast yellow tint.

What we claim is:

1. A monoazo-dyestuff of the pyrazolone series, which is free from sulfonic acid groups, contains a single carboxyl group and corresponds to the general formula in which one unsubstituted carbon atom is between X and the nearest of the other substituents. Y represents a member of the group consisting of a hydrogen atom, a chlorine atom and a methyl group, and X and Z each represent a sulfonamide group, of which groups at least one contains a hydrocarbon radical bound to the nitrogen atom and the hydrocarbon radicals contain together 3 to 9 carbon atoms.

2. A monoazo-dyestufi of the pyrazolone series which is free from sulfonic acid groups, contains a single carboxyl group, corresponds to the general formula in which X represents a sulfonamide group, which contains at least one hydrocarbon radical bound to the nitrogen atom but contains 3 to 9 carbon atoms.

3. The monoazo dyestufi of the formula HO 00011 I /CN o N=N-C 1 so NH H C=N 2 2 0:5 I

l CH3 1 I-oH2oHT-o112-0H3 H 4. The monoazo dyestufi of the formula /C--N N=NC 1 o Oz Hz l M o: I

CHz-CHg N-C CH1 I H CHr-CH 5. The monoazo dyestuff of the formula REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,821,933 Hentrich et a1 Sept. 8, 1931 1,908,571 Straub et a1. May 9, 1933 FOREIGN PATENTS Number Country Date 190,034 Switzerland June 16, 1937 189,041 Switzerland Apr. 16, 1937 210,605 Switzerland Oct. 1, 1940 

1. A MONOAZO-DYESTUFF OF THE PYRAZOLONE SERIES, WHICH IS FREE FROM SULFONIC ACID GROUPS, CONTAINS A SINGLE CARBOXYL GROUP AND CORRESPONDS TO THE GENERAL FORMULA 